Certain pyridyl silane derivatives



United States Patent This application relates to novel organosilicon compounds that are useful as sizing agents, elastomeric materials, etc.

The compounds of this invention include both silanes and siloxanes. Any silane of this invention can be de- -scribed as beinga compound of the formula Go (-R) nornornsin'. \N

where Q is a lower alkyl radicaL'R is a divalent radical free of aliphatic unsaturation selected from the group consisting of hydrocarbon radicals and radicals containing carbon, hydrogen, and oxygen in-an ether linkage, R is selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation, the hydroxyl group, and hydrolyzable groups, n is an integer of 0 to 1, and m is an integer of 0 to 2.

Q can be any lower alkyl radical such as methyl, ethyl, isopropyl, n-pentyl, or iso'hexyl.

R can be any divalent radical, as defined above, such as methylene, ethylene, propylene, decylene, octadecylene, 2,5-octylene,

halogen groups: F, 'Cl, Br, or I; or the isocyanate group.

.Thesiloxanes of this invention are. polymeric compositions containing at'leas't'one' unit of the formula:

where Q is a lower alkyl radical,R-is a divalent radical, free of aliphatic unsaturation, selected from the group consisting of hydrocarbonradicals and radicals containing carbon, hydrogen, and oxygen in an ether linkage, R is selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation, the hydroxyl group, and hydrolyzable groups, n is an integer of 0 to 1, and m and a are integers of 0 to-2, any other units present 'beingof the formula ZbSlO3 b 0 where Z is selected from the group'consisting of mono- R can be any monovalent hydrocarbon radical free of O(CH CH O) CH acyloxy groups such as formate, acetate, propionate or butyrate; ketoxime groups such as C=NO- valent hydrocarbon and halohydrocarbon radicals, and b is an integer of 0 to 3.

Examples of Q, R, and R are given above.

Z can be. any monovalent hydrocarbon radical; e.g., alkyl radicals such as methyl, ethyl, isopropyl, n-hexyl, Z-ethylhexyl, and octadecyl; unsaturated radicals such'as vinyl, ethynyl, allyl, butadienyl, -or S-hexenyl; cyclo- "aliphatic radicals such as cyclohexyl or cyclopentenyl; and aromatic containing radicals such as phenyl, tolyl, benzyl, fi-phenylpropyl, xenyl or naphthyl. Z can also be any monovalent halohydrocarbon radical; e.g. haloalkyl such as chloromethyl, 3,3,3-trifluoropropyl, ,B-(perfluoroheptyl) ethyl, or 4-bromohexyl; unsaturated radicals such as 3- chloroallyl or 4,4-difluorobutadienyl; cyclohaloaliphatic radicals such as chlorocyclohexyl or iodocyclopentenyl; and aromatic-containing radicals such as fluorophenyl, u,ct,a-trlfi1l01Ot01yl,0l chlorobenzyl.

The silanes of this invention can'be made by reacting as chloroplatinic acid and a suitable solvent such as xylene. If desired, a vin-yl polymerizationiinhibitor such as hydroquinone can also be added.

When n is zero, a CH CH group connects the 'pyridyloxy group to the silicon atom, i.e.

$ CHzCHzSiR's The siloxanes of this invention can be made by hydrolyzing and condensing silanes of this invention which contain hydrolyzable R groups. This hydrolysis reaction is well-known to the art. 4 v

A' pure form of silaue can be hydrolyzed to form siloxane hompolymers, or mixtures of silanes can be hydrolyzed to form siloxane copolymers. More than one species of silane of this invention can be cohydrolyzed, if desired, as can also other known silanes of the formula Z SiR' where Z and b are defined above, and R is a hydrolyzable group, as defined above.

The siloxanes of this invention can also be made by reacting V Qm Example 1 A composition consisting of 270.3 gfof 2-allyl0xypyridine, 268.5 g. of methyldiethoxysilarie, 248.6 g.' of xylene, and 2.0 g. of a solution of chloroplatinic acid in dimethylphthalate 1% by weight platinum) was refluxed at 130 to 143.5 C. for 27 hours.

On distillation there was recovered 198.9 g. of

'which has a boiling point of 165 C. at mm. Hg pressure, a viscosity at C. of 3.92 cs. and-an 1 of 1.4691.

A portion of this product was placed in a container with a large excess of distilled water and a small amount of KOH. On heating -at 100 C. for about 12 hours, a

prising units.

- viscous oil was formed which was a homopolymer co m-- is formed.

One mol (222 g.) of bis-[trimethylsiloxy]methylsilane was heated to 96 C. with 1 g. of chloroplatinic acid in isopropanol (1% Pt).

2-allyloxypyridine was added dropwise, the temperature being allowed to rise to 123 C., until one mole (135.5 g.) had been added.

The mixture was thenrefiuxed at C. for 12 hours.

A sizable yield of \N OCH2CH2CH2S[KOS1[CH3]3)2 CH3 was recovered.

Example 3 To 294.7 g. of phenyldimethylsilane, 2.3 g. of chloroplatinic acid in isopropyl alcohol 1% Pt), and 318 g. of xylene, there was added about 279 g. of 2-allyloxypyridine.

The mixture was refluxed for 42 hours from 120 to C.

7 On distillation, 118 g. of

o oHioHioHisi were recovered, as determined by nuclear magnetic resonance and infra-red spectra.

Example 4 When 0.2 mole of OC1H14CH=CH2 is heated with 0.1 mole of o1 in the presence of plantinum, a compound of the forinula oomoms uoonm 1 5 That which is claimed is: 1. A compound of the formula where Q is a lower alkyl radical, R is a divalent radical having from 1 to 18 inclusive carbon atoms, free of aliphatic unsaturation, selected from the group consisting of hydrocarbon radicals and radicals containing carbon, hydrogen, and oxygen in an ether linkage, R is selected from the group consisting of monovalent hydrocarbon radicals free of aliphatic unsaturation having from 1 to 18 inclusive carbon atoms, the hydroxyl group, and hydrolyzable groups selected from the group consisting of lower alkoxy groups, alkoxyalkoxy groups, acyloxy groups, ketoxime groups, halogen groups and isocyanate groups, n is an integer of to 1, and m is an integer of 0 to 2. 2.

W is Nf-O CHzCH2CHzSi(O CH5):

\N -oomomomsli 4. The composition of claim 1 where R is methylene. 5. The composition of claim 1, where at least 2 R groups are hydrolyzable groups.

References Cited UNITED STATES PATENTS 3,208,972 9/1965 Lyons 26046.5 3,215,666 11/1965 Simmler 260-465 3,218,330 11/1965 Duesel et al. 260297 3,223,710 12/1965 Greenhalgh et al. 260-297 JOHN D. RANDOLPH, Primary Examiner. WALTER A. MODANCE, Examiner. R. T. BOND, A. L. ROTMAN, Assistant Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,355,455 November 28, 1967 Loren A. Haluska It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, lines 58 to 64, the formula should appear as shown below instead of as in the patent:

o CH=CH2 Signed and sealed this 6th day of May 1969.

(SEAL) Attest:

M WARD M-FLETCHER,JR. W Attesting Officer ommis i er of aten s 

1. A COMPOUND OF THE FORMULA 